EP2956566A1 - Method for depositing a corrosion-protection coating - Google Patents

Abstract

The invention relates to the use of a cement in a method for pack-cementation deposition on a substrate containing cavities having a minimum equivalent diameter ecm, characterised in that the cement is formed by spherical particles each having a diameter d such that d ≤ ecm/10.

Description

 Method of depositing a coating against corrosion

The present invention relates to the production of a protective coating against corrosion on a substrate having cavities.

 The techniques of realization of coatings can be classified in three great families:

 - the thermal projection,

 chemical vapor deposition, and

 - the physical vapor deposition.

 Thermal spraying techniques such as plasma or flame projection involves sending molten or partially melted particles, at high speed, to the surface of the part to be protected. The coating is constructed in successive layers. These techniques can only be used on open or easily accessible surfaces.

 The vapor phase deposition techniques use a gaseous precursor of the coating to be produced. This precursor may be produced in the direct vicinity of the surface to be coated (carburized pack) or transported via a gas to the surface to be coated (out of pack, CVD from a bottle or gaseous mixture, etc.). The main difficulties encountered for the carburizing pack are related to the filling of parts having a complex geometry or very small dimensions (a few mm) with the cementum powder (precursor mixture of the coating). The main limitations of the techniques using gaseous precursors concern the rapid depletion of the gaseous mixture in reactive species resulting in heterogeneities of chemical composition and / or thickness of the coating. It is very difficult to obtain a homogeneous coating on large surfaces or in complex geometries.

 Physical vapor deposition techniques involve evaporating the component (s) of the coating prior to condensing them on the surface of the part to be coated. Evaporation is usually done by bombarding a target with a high energy beam (electrons or ions). The distance between the target and the surface to be coated is a major parameter for the homogeneity of the thickness of the deposit. These techniques are very difficult to use on parts of complex geometry or on non-accessible surfaces.

The intensification of industrial processes leads to the use of materials under increasingly stringent conditions and to reduce the size of the parts used. In most cases, it is necessary to protect the parts of their environment with a coating. As presented in the previous paragraphs, the complex geometries and non accessible surfaces pose problems for the realization of coatings with the traditional techniques.

 It is therefore necessary to develop new deposit techniques or adapt existing techniques to the new constraints.

 The carburizing pack is a very old process for making a coating on a part. The latter is placed in a bed of cementum powder, which is a mixture of products capable of generating a reactive atmosphere at high temperature. This cementum should be placed close to the surface to be coated to produce a homogeneous coating in thickness and chemical composition. Coatings are conventionally made on parts having cavities of a few centimeters by filling the part with the cementum powder.

 However, when the cavities have characteristic sizes of the order of a millimeter, and aspect ratios (ratio length / width) high, the introduction of the cement is much more complex. This is why processes using powder, type pack cementation are generally used for parts with no or little hard to access area.

 Therefore, a problem is to improve the deposition processes by pack cementation to allow their use for the substrate coating having cavities.

A solution of the present invention consists in the use of a cementum in a pack-cementation deposition process on a substrate having cavities of minimum equivalent diameter e _cm , characterized in that the cementum consists of spherical particles presenting each a diameter d such that d <e _cm / 10.

 The size of the cement particles can be measured by laser granulometry or sieves to ensure that no particle or agglomerate of cement particles exceeds the maximum size required.

 A disagglomeration step may be necessary to "break" the agglomerates of elementary particles that may exceed the maximum size required.

 The equivalent diameters of the particles are conventionally comprised between Ιμιη at 1 mm, preferably between Ιμιη at ΙΟΟμιη.

The equivalent diameter is defined as the diameter of the cylinder or circle that fits into the smallest section giving access to the surface to be coated. Indeed, the latter does not necessarily have a standard form. Depending on the case, the use according to the invention may have one or more of the following characteristics:

the cementum consists of spherical particles each having a diameter d such that d <e _cm / 10.

 the cementum comprises a precursor of the element to be deposited, an activating agent and an inert diluent

 the cementum comprises 10 to 60% of metal powder as precursor of the element to be deposited, 5 to 40% of activating agent, and a complement of 100% of inert diluent, the inert diluent preferably comprising refractory oxides,

the metal powder is made of aluminum or a mixture of aluminum with particles of Ni _x Al _y or of

 the cementum comprises a precursor of the element to be deposited, a stripping flux, and an inert diluent.

 the cement comprises an organic or inorganic binder. The organic binder may be PVA polyvinyl acetate and the inorganic binder may be SiO 2. Indeed, the organic or inorganic binder be used during a step of atomizing the powder mixture. This optional step improves the flowability of the powder and thus the filling of the piece. It is to form spherical agglomerates of the powder mixture. This step will preferably be carried out under an inert atmosphere in order to prevent the surface oxidation of the metal powders which may be harmful for the deposition.

 The inert compound does not chemically intervene in the formation of the coating. Its main function is to avoid the densification of the cementum which would prevent its elimination after deposit. It is usually a very stable refractory compound. Its content is the complement of the other two.

 The solution according to the invention allows the realization of a deposit by pack cementation on parts of complex geometry and in inaccessible cavities.

 The cementum used in the context of the invention has a very good flowability to fill the smallest gaps (diameter <1mm) and distribute evenly within the entire cavity to be coated. The particle size distribution and the morphology of the cement particles are the main parameters to ensure a good flowability of the mixture.

The particle size distribution is adjusted according to the equivalent diameter of the smallest passage of the cavity. With regard to morphology, spherical shapes which can be obtained by different grinding techniques for powders or powder mixture. An atomization treatment of the powder mixture may also be used to form spheres of the powder mixture. In the latter case, organic additives may be used to ensure a good cohesion of the spheres and a homogeneous dispersion of the elements of the mixture.

The present invention also relates to two methods of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm .

The first method of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm comprises the following successive steps:

a) preparing a cementum consisting of spherical particles of an activating agent, an inert diluent and a metal powder, said spherical particles each having a diameter d such that d <e _cm / 10;

 b) introducing into the cavities of the substrate the cementum prepared in step a) by a vibratory system;

 c) the substrate-cement element is heated to a temperature below the melting temperature of the metal powder for a period of at least 6 hours at about 650 ° C for aluminum.

 d) the substrate-cement element is cooled to room temperature

 e) the cementum is subjected to a vibration step so as to eliminate the cement residue,

 f) the substrate-cement element is heated to a temperature of between 900 ° C. and 1150 ° C., preferably greater than 980 ° C., and

 g) recovering a substrate having a coating as a whole.

 For example, if the metal powder is aluminum, in step c) the substrate-cement element is heated at about 650 ° C. for at least 6 hours.

 Depending on the case, the first method may have one or more of the following characteristics:

 the particles of the cementum prepared in step a) are pre-activated by mechano-synthesis; preactivation makes it possible to increase the chemical reactivity of the precursor particles.

This treatment facilitates the reaction between the precursor and the activator and therefore the deposition.

 the coating recovered in step g) comprises NiAl;

 the coating recovered in step g) has a thickness of between 15 and

25 μιη. The second method of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm comprises the following successive steps:

a) a cementitious consisting of a stripping flux and spherical particles of an inert diluent and a metal powder is prepared, said spherical particles each having a diameter d such that d <e _cm / 10;

 b) introducing into the cavities of the substrate the cementum prepared in step a) by a vibratory system;

 c) the substrate-cementation unit is heated to a temperature above the melting temperature of the pickling stream, under a primary vacuum or under an inert atmosphere (Ar), for a period of between 10 min and 2 h;

 d) the substrate-cement element is cooled to room temperature

 e) the cement is subjected to a washing step so as to remove the cement residue;

 f) recovering a substrate having on its assembly a coating.

 As the case may be, the second method may have one or more of the following characteristics:

 the washing step e) is carried out by means of an acidified aqueous solution.

the coating recovered in step f) comprises NiAl ₃ .

 said process comprises, before step e), a step of heating the substrate-cementation unit at a temperature of between 900 ° C. and 1150 ° C., preferably greater than 980 ° C.

 the coating recovered in step f) comprises NiAl.

 - The coating recovered in step f) has a thickness between 5 μιη and 200μιη, preferably between 5 μιη and 80 μιη.

 Figure 1 shows schematically the different steps of the first method according to the invention.

The first process consists in the use of a powder mixture consisting of the activating agent (5%), an inert diluent (Alumina, silica, etc.) and a metal to be deposited, a metal powder ( between 10 and 60%) which may be either pure aluminum or an Al + NIA1 or AlCr mixture and whose particles may or may not have been "pre-activated" by mechano-synthesis.

The granulometry of the mixture is then adjusted so that it can be introduced into the channels by a vibratory system. The assembly is then brought to a temperature below the melting temperature of the metal to be deposited for a period of at least 6 hours. After cooling, the assembly is again subjected to a vibration step for extracting the residual powder. At this stage, the coating consists of a surface enrichment of aluminum substrate whose composition is close to NiAl ₃ . The thicknesses obtained vary between 5 and 10 μιη depending on the time during which the first heating step was carried out. After this step, the part thus coated is brought to a temperature of between 900 ° C. and 1150 ° C., preferably greater than 980 ° C., so as to obtain the NiAl composition in a superficial edge of thickness ranging from 15 to 25 μm ( Figure 3).

FIG. 2 schematizes the different steps of the second method according to the invention. The second method consists in the use of a powder mixture consisting of a low-melting pickling flux (K A1F ₆ -KA1F ₄ ) which is the element which has the lowest melting point of the mixture constituting the cement and particles of an inert diluent and a pure metal powder or aluminum alloy. (10 to 60% of metal powders, 40% of stripping flux and the balance of inert diluent).

 The whole is introduced by vibration as in the case of the first method and is heated to a high temperature, lower than the melting of the metal phase, but greater than that of the stripping flux for a time that varies from a few minutes to one or two hours. .

 Note that the coating is obtained either under primary vacuum or inert controlled atmosphere (argon).

 The residues are then extracted by washing directly after the heat treatment step. To further improve the extraction of residues, the apparatus can be washed with a chemical solution (acidified aqueous). The coating thus obtained corresponds to a phase of composition close to NiAl which can be converted into NiAl in a subsequent annealing step at a temperature between 900 ° C and 1150 ° C, preferably at 980 ° C. The appearance of the coating is shown in FIG.

 The powder mixtures can be stored for long periods of time in a desiccator under a primary vacuum or in a dry chamber under a neutral gas sweep and are immediately ready for use.

 Preferably, the inert diluent is selected from powders of refractory inert materials, more preferably from refractory mineral oxides, such as alumina, silica, magnesia and mixtures thereof, which are commonly used in cementation.

The substrate which can be provided with such a coating is generally chosen from metal substrates, for example iron or nickel base, alloy (s) substrates or superalloy (s), composite substrates comprising one or more metals and / or alloy (s) and / or superalloy (s) containing Ni to react with the deposited Al and form NiAl.

 Depending on the desired coating thickness, the substrate may be previously superficially enriched in Ni for example by electrolytic deposition.

 By way of examples of parts on which the deposition processes according to the invention can be implemented, mention may be made of the interior of tubes, turbine blades, heat exchangers, in particular metal heat exchangers, reactor exchangers, storage capacities, ....

 The treatments are generally carried out under a neutral or reducing atmosphere, for example under an atmosphere of hydrogen and / or argon, preferably under an argon atmosphere, or under an argon atmosphere with, for example, from 5 to 10% of argon. hydrogen.

The pressure used during the treatment may be atmospheric pressure or a reduced pressure, for example a pressure of 10 ^" atm of argon.

 The coatings obtained by the processes according to the invention give the substrates an excellent resistance to corrosion, even within each substrate cavity regardless of its size.

 As a result, the service life of these substrates is substantially improved.

EXAMPLE

The photos of FIG. 3 show two samples of HR120 alloy, one (the one on the right) coated with the coating produced according to the second method according to the invention and the other (the left one) uncoated. These samples were subjected to a corrosive atmosphere consisting of (in% vol.): 15% CO, 5% CO ₂ , 55% H ₂ , 25% H ₂ O, at a pressure of 21 bar absolute and a temperature of 650 ° C. After 4700 hours of exposure, it is clear that the coating deposited according to the second method of the invention can protect the alloy from corrosion.

Claims

claims 1. Use of a cementum in a deposition process by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm , characterized in that the cement consists of spherical particles each having a diameter d such that d e e _cm / 10. 2. Use according to claim 1, characterized in that the cementum consists of spherical particles each having a diameter d such that d <e _cm / 10. 3. Use according to one of claims 1 or 2, characterized in that the cement comprises a precursor of the element to be deposited, an activating agent and an inert diluent. 4. Use according to claim 3, characterized in that the cement comprises: 10 to 60% of metal powder as precursor of the element to be deposited,  5 to 40% of activating agent, and  a complement to 100% of inert diluent. 5. Use according to claim 4, characterized in that the metal powder is made of aluminum or a mixture of aluminum with Ni _x Al _y particles or Alx'Cry '. 6. Use according to one of claims 1 or 2, characterized in that the cement comprises a precursor of the element to be deposited, a stripping flux, and an inert diluent. 7. Use according to one of claims 1 to 6, characterized in that the cement comprises an organic or inorganic binder. 8. Use according to one of claims 1 to 7, characterized in that the substrate is a metal heat exchanger. 9. A method of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm , comprising the following successive steps: a) preparing a cementum consisting of spherical particles of an activating agent, an inert diluent and a metal powder, said spherical particles each having a diameter d such that d <e _cm / 10;  b) introducing into the cavities of the substrate the cementum prepared in step a) by a vibratory system;  c) the substrate-cement material is heated to a temperature below the melting temperature of the metal powder for a period of at least 6 hours to approximately 650 ° C for aluminum.  d) the substrate-cement element is cooled to room temperature  e) the cementum is subjected to a vibration step so as to eliminate the cement residue,  f) the substrate-cement element is heated to a temperature of between 900 ° C. and 1150 ° C, preferably greater than 980 ° C, and  g) recovering a substrate having a coating as a whole. 10. Deposition process according to claim 9, characterized in that the particles of the cementum prepared in step a) are pre-activated by mechano-synthesis. 11. The deposition method according to one of claims 9 or 10, characterized in that the coating recovered in step g) comprises NiAl. 12. deposition process according to one of claims 9 to 11, characterized in that the coating recovered in step g) has a thickness between 15 and 25 μιη. 13. A method of depositing a coating by pack cementation on a substrate having cavities of minimum equivalent diameter e _cm , comprising the following successive steps: a) a cementitious consisting of a stripping flux and spherical particles of an inert diluent and a metal powder is prepared, said spherical particles each having a diameter d such that d <e _cm / 10; b) introducing into the cavities of the substrate the cementum prepared in step a) by a vibratory system;  c) the substrate-cementation unit is heated to a temperature above the melting temperature of the pickling stream, under a primary vacuum or under an inert atmosphere (Ar), for a period of between 10 min and 2 h;  d) the substrate-cement element is cooled to room temperature  e) the cement is subjected to a washing step so as to remove the cement residue;  f) recovering a substrate having on its assembly a coating. 14. The method of claim 13, characterized in that the washing step e) is carried out by means of an acidified aqueous solution. 15. Method according to one of claims 13 or 14, characterized in that the coating recovered in step f) comprises NiAl ₃ . 16. Method according to one of claims 13 or 14, characterized in that said method comprises before step e) a step of heating the substrate-cement unit at a temperature between 900 ° C and 1150 ° C, preferably greater than 980 ° C. 17. The method of claim 16, characterized in that the coating recovered in step f) comprises NiAl. 18. Method according to one of claims 13 to 17, characterized in that the coating recovered in step f) has a thickness between 5 μιη and 200μιη, preferably between 5 μιη and 80μιη. 19. Method according to one of claims 9 to 18, characterized in that the substrate is a metal heat exchanger.